Cationizable rheology modifying and setting means, composition thereof and method of making both

Abstract

Provided are: a copolymer for rheological or cosmetic compositions and, a composition thereof, and methods of making and using the same. Said copolymer comprises a) a first acrylic ester as monomer A, said monomer A being a branched acrylic ester; b) at least one further acrylic ester as monomer B, said monomer B being a linear acrylic ester; c) a cyclic N-vinyl amide as monomer C; d) at least one compound comprising a radically polymerizable .-ethylenically un-saturated double bond and at least one cationic and/or cationogenic moiety said compound being monomer D; e) at least one monoethylenically unsaturated carboxylic acid as monomer E; with the monomer B in its polymerized form having a glass transition temperature of 24 C. or lower and making at most one third of the weight amount of monomer A.

Claims

1. A copolymer for rheological or cosmetic compositions comprising: a) 30 to 50% by weight tert-butyl acrylate as monomer A; b) 3 to 20% by weight acrylic ester as monomer B, wherein the monomer B has an ester moiety, wherein the ester moiety is COOC.sub.1-C.sub.14-alkyl; c) 15 to 35% by weight N-vinyl pyrrolidone as monomer C; d) 15 to 30% by weight N-[3-(dimethylamino)propyl]methacrylamide being monomer D; e) 0.1 to 10% by weight methacrylic acid as monomer E; with the monomer B in its homopolymerized form having a glass transition temperature of 24 C. or lower and making at most one third of the weight amount of monomer A, wherein: a sum of monomer B and monomer E does not exceed 20% by weight of the total copolymer weight, a sum of monomer C and monomer D ranges between 45% by weight and 75% by weight of the total copolymer weight, and the monomer D is used in a weighting excess with respect to monomer E, said weighting excess being at least three and one half times the weight amount of monomer E, with the proviso that the total copolymer weight is the sum of the weight amounts of monomers A to E and corresponds to 100% by weight.

2. A composition comprising at least: water and/or aVOC and the copolymer according to claim 1; wherein the amount of the copolymer used ranges from 0.001 to 50% by weight, with respect to the total weight of the composition, said total weight corresponding to 100%.

3. The composition according to claim 2 that is effective: for hair styling and/or hair conditioning, for body care products, as rheology modifier in construction materials; or in agricultural formulations or plant protection formulations.

4. The copolymer according to claim 1 wherein the ester moiety of monomer B is COOC.sub.2- C.sub.12-alkyl.

5. The copolymer according to claim 1 wherein the ester monomer B is selected from the group consisting of n-butyl acrylate, lauryl acrylate, and ethyl acrylate.

Description

(1) Further features, details and advantages of the invention result from the claims' wording as well as from the following description of embodiments and drawings.

(2) FIG. 1 shows the visual aspect of propellant supplemented polymer solution reference samples.

(3) FIG. 2a shows the microscopic surface structure of untreated Caucasian hair.

(4) FIG. 2b shows the microscopic surface structure of hair treated with Amphomer.

(5) FIG. 2c shows the microscopic surface structure of hair treated with a composition comprising a copolymer as specified in comparative example V3 or V4.

(6) FIG. 2d shows the microscopic surface structure of a hair treated with a composition comprising an inventive copolymer.

(7) FIG. 2e shows a compilation of FIGS. 2a through 2d.

PREPARATION OF THE COPOLYMER

(8) The preparation of a typical inventive copolymer makes reference to example 1 in table 1 infra and is realized by means of solution polymerization in an isopropanol/water mixture.

(9) Feed 1:

(10) 640 g of 1-Vinyl-2-pyrrolidon

(11) 296 g of N-[3-(Dimethylamino)propyl]acrylamide

(12) 71 g of Methacrylic Acid

(13) Feed 2:

(14) 948 g of tert.-Butylacrylate

(15) 296 g of N-[3-(Dimethylamino)propyl]acrylamide

(16) 118.5 g n-Butyl acrylate

(17) Feed 3

(18) 2.5 g of 2,2-Azobis(2-methylbutyronitril) in 300 g of ethanol

(19) Feed 4

(20) 7.5 g of 2,5-Bis(tert.-butylperoxi-2,5-dimethylhexane) with the trade name Trigonox 101 of Akzo Nobel in 500 g of ethanol

(21) Feed 5

(22) 104 g of phosphoric acid (50% w/v in isopropanol)

(23) viz. 201.4 g of feed 1, 1/13 viz. 104.8 g of feed 2 and 1/15,125 viz. 20 g of feed 3 and 300 g of a mixture of isopropanol/water having a ratio of 1:1 v/v were placed in a stirring means equipped with reflux condenser and three distinct inlets for feeds 1 through 3 and said mixture was heated up to 75 C. while stirring. Once copolymerization had started, which was observed by the initial increase of the mixture's viscosity, the remainder of feed 1 was added in between 1 h, the remainder of feed 2 was added within 4 h and the remainder of feed 3 was added within 5 h while increasing the inner temperature of the means up to 80 C. Once feeding terminated copolymerization was continued for another two hours at said temperature.

(24) Feed 4 was then added within 2 h and further copolymerization was realized for another 10 h at 130 C. under inherent pressure, in order to diminish the amount of residual monomers. (In an alternative the remainder of monomers is to be reduced by means of supplementing water and phosphoric acid to the mixture and subsequent heating thereof of up to 100 C., with phosphoric acid being added in such amount that a pH ranging from 4.5 to 5.5 is reached, which corresponds to a degree of neutralization of the N-[3-(Dimethylamino)propyl]acrylamide used ranging from 80 to 120 mol %.) Subsequently a steam distillation is realized.

(25) Once the mixture being cooled down it is neutralized by means of feed 5, which is supplemented in between 30 min with continuous stirring.

(26) The copolymer solution thus obtained is susceptible to be supplemented with further water after which isopropanol is to be removed by distillation in order to yield aqueous (micro)dispersions of the inventive copolymer. Powdery embodiments of the inventive copolymer are obtained by means of spray drying or lyophilization.

(27) Further inventive copolymers are to be obtained by the previously given protocol however respecting the required monomers and quantities inter alia indicated in table 1 infra.

(28) Preparation of a Cosmetic Composition of the Invention

(29) A typical inventive cosmetic composition among other such inventive compositions is prepared as follows: The inventive copolymer is dissolved in the required amount of ethanol to give a 5% by weight solution. Thus also a copolymer solution per se is understood to be an inventive composition

(30) The aspect of the copolymer solution is to be monitored by a testing panel of five persons. They evaluate the appearance of the rheological or cosmetic composition further its homogeneity and its colour.

(31) The appearance is determined to be clear (1), almost clear (2), clouded (3) or turbid (4).

(32) The homogeneity of the copolymer solution dried on a glass plate as a copolymer film was determined by a testing panel of five persons and evaluated on a scale from 1 to 4 with:

(33) 1=very homogenous film, no inclusions

(34) 2=homogenous film with very small irregularities

(35) 3=homogeneous film showing already some aberrations

(36) 4=irregular structure almost no continuous film

(37) Compatibility with propellant is assessed by applying a propellant gas to a solution containing the inventive polymer and comparing it with reference samples as shown in FIG. 1. The solution chosen and the concentration of the inventive polymer therein are identical for the inventive copolymer and the reference samples. Likewise the pressure and type of propellant gas employed are identical. Compatibility is determined as follows:

(38) 1=excellent compatibility, solution remains limpid and mobile, cf. left bottle of FIG. 1

(39) 2=good compatibility, solution is slightly turbid and mobile cf. second bottle from the left of FIG. 1

(40) 3=moderate compatibility, solution is turbid, less mobile as in third bottle from the left of FIG. 1

(41) 4=poor compatibility, solution is opaque and has a higher viscosity, cf. right bottle of FIG. 1

(42) Determination of the Stiffening Effect of a Copolymer Solution Treated Hair Strand:

(43) 1 g of copolymer solution was applied onto a hair strand having a length of approximately 23 cm and spread in the hair strand's direction with the fingers. Said strand was dried over night at room temperature and analyzed by a test panel of five persons the next day. The results obtained are ranged as follows:

(44) 1=very good stiffening effect

(45) 2=good stiffening effect

(46) 3=still good stiffening effect

(47) 4=poor stiffening effect

(48) Washability was determined as follows: A hair strand treated with a respective copolymer solution of the invention is washed in a 37 C. solution containing Texapon-NSO (CAS 68891-38-3) by soaking it and squeezing it for 15 sec. This is repeated five times. Thereafter the strand is rinsed for 15 sec. with tab water. This soaking, squeezing and rinsing is once repeated. The strand is then squeezed onto filter paper and dried over night. The washability will be determined the next day. Parameters evaluated by the test panel of five persons are the strands ability to be combed, its tendency to stick, its sensation when grasped and the quantity of composition residues

(49) The results obtained are:

(50) TABLE-US-00001 very good (1) all parameters are excellent good (2) at least three of the four parameters are excellent still good (3) two of the parameters are excellent not good (4) does not meet the previously mentioned criteria
Determination of the Flexural Strength Bt of a Hair Strand Treated with a Hair Styling Composition of the Invention:

(51) A dried hair strand having a length of 24 cm was weighed. 3 g thereof were immersed in the copolymer solution previously prepared, removed thereof and excess solution was stripped. Immersing, removing and stripping was realized three times in order to achieve a homogeneous repartion of the solution in the hair strand.

(52) The last stripping of excess solution was done with thumb and forefinger. Further removal of the solution was realized by pressing the hair strand between filter paper such that the hair strand's weight increases by 1 to 1.4 g (with regard to the initial weight of the hair stand). The strand thus obtained was arranged in order to have a round cross-section and was stored at 20 C. and 65% of relative humidity over night in a climatic chamber.

(53) Analysis of the strand prepared was realized in the climatic chamber having the climatic conditions mentioned before by means of a pull and compression analyzer (Easytest 86 8002, Fa. Frank). The hair strand was placed in a symmetrical way on two cylindrical rolls of the sample holder, said rolls having a diameter of 4 mm and being separated from each other by a distance of 9 cm). By means of a rounded stamp approached from the upper side of the strand and in the exact middle thereof the strand was bent by 40 mm which leads to fracture the copolymer film obtained on the strand. The force required therefore is determined in cN by means of a load cell.

(54) Microstructure, Flaking: A hair strand is subjected to electron microscopy (light microscopy). The results obtained are grouped as follows: clumpy/clumsy: formations of bulky copolymer aggregates on the hair flaky: occurrence of copolymer flakes on the hair surface or hair pellicle regular: finely dispersed copolymer film on the hair capable of maintaining the surface microstructure of the treated hair.

(55) TABLE-US-00002 TABLE 1 Ex. MMA OAM tBAEMA AS HPMA V1 35 40 6 15 5 TBA VP DMAPAM MAS Fifth Siloxane Monomer V2 30 27 17* 5 19% 2 nBA TBA VP DMAPMAM MAS Fifth Siloxane Monomer V3 50 28 15 6 1 V4 45 27 25 3 1 40 27 25 3 5% nBA 2 35 27 25 3 10% nBA 3 40 27 25 3 5% LA 4 40 27 25 3 5% EA MMA Methylmethacrylate OAM: Octylacrylamide tBAEMA 2-(tert.-Butylamino)ethyl methacrylate AS Acrylic Acid HPMA Hydroxypropylmethacrylate TBA tert.-Butylacrylate VP 1-Vinyl-2-pyrrolidon DMAPAM N-[3-(Dimethylamino)propyl]acrylamide DMAPMAM N-[3-(Dimethylamino)propyl]methacrylamide MAS Methacrylic Acid nBA n-Butyl acrylate LA Lauryl acrylate EA Ethyl acrylate Siloxane ethoxylated polysiloxane (Belsil DMC 6031 of Wacker Chemie GmbH) INCI Name: PEG/PPG-25/25 Dimethicone viz. the alkoxylated derivative of Dimethicone (q.v.) containing an average of 25 moles of ethylene oxide and 25 moles of propylene oxide

(56) TABLE-US-00003 TABLE 2 Aspect Homoge- Compat- Co- neity Co- ibilty Stiff- Flexural polymer polymerfilm with ening Wash- strength Ex. Solution on Glass Plate Propellant Effect ability [cN] V1 1 1 1 1-2 2 165 V2 1-2 1-2 1-2 1 V3 1 1 1 2 3 185 V4 4 3 3-4 nd 1 1 2 1 1-2 2 255 2 1 1 1 1-2 3 210 3 1 1 1 1 2 527 4 1 1 1 1 2 516 nd The flexural strength cannot be determined

(57) TABLE-US-00004 TABLE 3 Spraying Copolymer Portion Pattern required to Plas- Elas- Particle Mikro- obtain a defined Ex. ticity ticity Size [m] structure/Flaking flexural strength V1 0.06 0.51 89 clumpy/clumsy 1 V2 1 V3 0.65 57 flaky 1 V4 flaky 1 1 0.91 0.65 41 regular ~ 2 0.9 0.65 63 regular ~ 3 0.89 33 regular ~ 4 0.79 35 regular ~

(58) All solvents (water and/or VOC) typically used in an inventive composition of the copolymers of the invention confer to said composition a clear aspect which can be gathered from table 2 column 2. Said results were obtained with an ethanolic solution of the inventive copolymer as previously indicated. One observes that the results are better or at least identical to those of the comparative experiments. However, comparative example V4 is shown to largely under-perform. Similar results were obtained with methanol or with isopropanol.

(59) All copolymers of the invention exhibit a tendency to form very regular films on a glass plate (cf. table 2, column 3). For all except one of the exemplified copolymers very homogeneous films with no inclusions are obtained and one thereof provides a homogenous film with very small irregularities. Thus the requirements of the comparative examples could be easily met and in some cases even be outperformed.

(60) A further very important issue is the inventive compositions' compatibility with respect to propellants. The visual impact of such compatibility is shown in FIG. 1 and one can observe that especially in transparent containers or on dark hair, compositions as shown in the outer right bottle of said FIG. 1 are not acceptable. Column 4 of table 2 shows all exemplified copolymers to perform extraordinary since the respective pressurized solution remains limpid and mobile. This is at least equal to some of the comparative examples but mostly far better. However, comparative example V4 shows a pretty bad result in this regard.

(61) The inventive compositions' ability to stiffen a hair do is good to very good and outperforms comparative example V3 (cf. column 5 of table 2).

(62) The washability is shown to be better or at least similar to this one of the comparative examples V1 to V4. This assures a long lasting styling and conditioning effect even in stormy or rainy weather

(63) The flexural strength provides a means for monitoring the rigidity or flexibility of a copolymer film formed on a hair do or a copolymer layer located within a cosmetic composition like for instance a cream. More the value is high more a film or a layer can be bent without causing partial or total fracture thereof. Thus high values are highly preferable since they protect a headdress or a cosmetic composition or a surface subjected therewith from mechanically caused damage. Column 7 in table 2 shows that every exemplified cosmetic composition outperforms the comparative examples.

(64) Regarding plasticity in column 2 of table 3, only values for some examples and comparative examples were recorded or obtained. Despite the incompleteness of these data it can however be observed that results obtained for inventive compositions are more than ten times larger compared to comparative examples.

(65) Likewise the elasticity of the films or surfaces evolving from the inventive cosmetic compositions is mostly approximately 20% or more elevated and at least comparable to the comparative examples.

(66) One prerequisite for forming a homogeneous regular and thin copolymer film on a ceratinic surface like hair or on the skin is to finely spread the respective cosmetic composition onto the destined surface. This can be assured by forming small droplets either within an emulsion or within an atomized spray. However said droplet size depends on the cosmetic composition and in particular on the inventive copolymer incorporated therein. In this regard the inventive compositions forming droplets having a particle size of 33 and 41 outperform the comparative examples and example 2 only shows a slightly larger particle size or droplet size compared to comparative example 3 (cf. column 4 of table 3).

(67) For the invention disclosed herein great emphasize was given to avoid flaking which is easily observed with dark hair. In this same context a clumpy or clumsy aspect of the treated hair, ceratinic surface or skin should also be avoided, since this prevents from conferring to said hair, ceratinic surface or skin a smooth and glossy non-sticky feel and a fine appearance not disturbed by clumpy or clumsy copolymer aggregates. To establish the potential of the inventive compositions in this regard LM-micrographs were recorded (cf. FIG. 2a to e).

(68) FIG. 2a depicts untreated Caucasian hair. A normal finely layered slate roof structure of ceratinic blocks can be observed.

(69) In FIG. 2b an ethanolic solution of the commercially available copolymer Amphomer (CAS-No. 70801-07-9) was applied as cosmetic composition of the prior art to said Caucasian hair. One observes in the right part of said figure a clumsy polymer aggregate completely covering the slate roof structure of the untreated hair. Such heterogeneous polymer repartition yields a sticky sensation and a dim and dull aspect of the hair style. Styling cannot be as efficient as it might be and thus more cosmetic composition and in particular polymer is required in order to obtain the same styling effect. Furthermore, such microscopically huge aggregates are prone to at least partially decompose as a result of mechanical stress, which would result in flaking to at least some extent.

(70) Untreated Caucasian hair is treated in FIG. 2c with a composition comprising a copolymer as specified in comparative example V3 or V4. It is to be noted that compositions comprising such polymer are able to conserve the slate roof structure of untreated hair. However, an increased amount of flakes is observed, which makes the use of such cosmetic composition somewhat unpleasant especially for dark haired people. This is still to be ameliorated.

(71) The hair strand exposed in FIG. 2d was treated with a cosmetic composition of an inventive copolymer. Similar to FIG. 2c the slate roof structure of untreated hair is properly maintained. However, this is achieved without any detrimental flaking phenomenon. Thus a cosmetic composition comprising the newly developed family of inventive copolymers is also readily applicable for the huge quantity of dark-haired people.

(72) The aforementioned results can be recapitulated from FIG. 2e making a compilation of FIGS. 2a to 2c. They are also listed in column 5 of table 3.

(73) Another important aspect of the invention was to improve the prior art with respect to costs of the copolymer used for styling purposes. Column 6 in table 3 shows the amount of copolymer to be required for one and the same styling result to be dramatically decreased for the inventive embodiments. At most of the amount required in the comparative examples and at best only thereof is needed when employing inventive embodiments.

(74) One observers that the present invention deals with a copolymer for rheological or cosmetic compositions, a process of making it, a composition thereof and a method of producing said composition. Also within the scope of the invention are selected uses of either the copolymer or the composition thereof. Said copolymer comprises a) a first acrylic ester as monomer A, said monomer A being a branched acrylic ester; b) at least one further acrylic ester as monomer B, said monomer B being a linear acrylic ester; c) a cyclic N-vinyl amide as monomer C; d) at least one compound comprising a radically polymerizable .-ethylenically un-saturated double bond and at least one cationic and/or cationogenic moiety said compound being monomer D; e) at least one monoethylenically unsaturated carboxylic acid as monomer E; with the monomer B in its polymerized form having a glass transition temperature of 24 C. or lower and making at most one third of the weight amount of monomer A.